CN103061162B - A kind of degradable composite material prepreg cloth and preparation method thereof and device - Google Patents
A kind of degradable composite material prepreg cloth and preparation method thereof and device Download PDFInfo
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Abstract
The present invention relates to a kind of degradable composite material prepreg cloth and preparation method thereof and device, this composite material presoaked cloth is made up of polydactyl acid (PLA) resin, natural fiber, and wherein polydactyl acid (PLA) resin accounts for 40～70% (weight) of composite material presoaked cloth；This preparation method comprises the following steps: after continuously natural fiber is dried and waits and process, with melted modified PLA dipping, modified PLA is coated in surface of natural fibers, through roll-in, cools down rolling and obtains；This device includes unwinding machine, beaming appliance of arranging, direction-control apparatus, hold-down roller, tenslator, film extruder, impregnation chiller, wrap-up etc..Compared with prior art, the present invention has the advantages such as Fiber Aspect Ratio is big, PLA reinforced effects is obvious, screw rod abrasion little, technique simple, the energy-conserving and environment-protective of extruder.
Description
Technical field
The present invention relates to polymer composite and preparation method thereof and device, particularly relate to a kind of degradable composite material
Prepreg cloth and preparation method thereof and device.
Background technology
Polylactic acid (PLA) does not exist at nature, is that the lactic acid obtained after the fermentation such as Semen Maydis, Rhizoma Solani tuber osi is aggregated
Form.Polylactic acid has good biodegradability, can gradually degrade under natural environment, generates water and carbon dioxide, its
Degradation process will not produce secondary pollution to environment；And along with the minimizing of oil content, with oil as main material production
Various polymer raw material prices rise steadily, and as circulation rate PLA faster price along with production technology development and
The progress of science and technology, price will be more and more lower, its as the effect of the succedaneum of oil product by increasing.The mechanics of PLA
Intensity includes that hot strength, bending strength higher than general purpose polypropylene (PP), meet the standard of civilian plastic strength, but its intensity
Need nonetheless remain for continuing to improve, to expand the range of application of PLA, improve its intensity.In terms of the toughness reinforcing of PLA and enhancing modified, grind
Studying carefully personnel and done substantial amounts of research, wherein Research on Toughening is predominantly added various toughener and is improved fracture fragility；It strengthens research
Aspect, predominantly adds various chopped strand or inorganic filler, and after strengthening, composite can not be degradable.
The mechanical property of natural fiber/PLA composite is higher than pure PLA, and the purer PLA of price of natural fiber material is cheap, can
To reduce production cost.Although natural fiber strength with rigidity compared with glass fibre, also a certain distance, but due to material
The density of material is relatively low, low price, and has good biodegradability, is widely used to industrial circle at present.
For preparing degradable PLA reinforcing material, Ren Jie etc. uses atural staple fibre or natural long fibre (to include Boehmeria
Fiber, linen fiber, tossa etc.) carry out melt blending extrusion, natural fiber/PLA that preparation can be degradable with PLA
Composite.In patent 200610037894.7, natural fiber and PLA and antioxidant, nucleator, lubricant are mixed by Dong Weiwei
Close, through melt extruding pelletize, obtain product.The Fiber Aspect Ratio of natural fiber reinforcing material prepared by this method is less,
Its reinforced effects is limited；And the screw rod of extruder is had bigger abrasion.In patent 200610070280, Fang Kun uses mixing
The method of yarn is prepared continuous glass fibre and is strengthened the pellet of PP, is helped with PP resin and processing by the compound mixed yarn containing glass fibre
Agent mixes, and heats melt blending, extruded machine extruding pelletization.The product that profit is produced in this way can fully regulate enhancing
The content of fiber, but this method is through extruding pelletization, and formation is chopped pellet, it is impossible to forms continuous print and strengthens preimpregnation
Band.And this kind of method is unsuitable for producing natural fiber and strengthens PLA.First PLA easily degrades, through a spinning moulding,
The mechanical property of PLA can decline, then through a heating process, the degraded of PLA is obvious；Secondly natural fiber is with glass fibre not
With, glass fibre is artificial fiber, can effectively improve the length of fiber, but natural fiber has to pass through twisting and could be formed
Effectively continuous.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of and can form continuous sky
The degradable composite material that right fiber/PLA, Fiber Aspect Ratio are big, PLA reinforced effects is obvious, the screw rod abrasion of extruder is less
Prepreg cloth and preparation method thereof and device.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of degradable composite material prepreg cloth, this composite material presoaked cloth includes polydactyl acid (PLA) resin, natural
Fiber, wherein polydactyl acid (PLA) resin accounts for the percentage by weight of composite material presoaked cloth is 40～70%.
Described polydactyl acid (PLA) resin uses following methods to obtain: by polylactic acid (PLA) resin 70～100 weight
Amount part, antioxidant 0～5 weight portion, bulking agent 0～10 weight portion, weather resisting agent 0～3 weight portion, releasing agent 0～5 weight portion, resistance
Combustion agent 0～5 weight portion, other auxiliary agent 0～2 weight portions mix 3～7 minutes in a mixer, join double after being sufficiently mixed
Screw extruder extrusion pelletizing, screw speed is 10～250r/min, and extrusion temperature is 150～210 DEG C, obtains polydactyl acid
(PLA) resin.
The melt index of described polydactyl acid (PLA) resin is 10～40g/10min, viscous equal molecular mass preferably 1
～10 × 105g/mol。
Described antioxidant be selected from four { β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid } pentaerythritol ester, (3,5-bis-
Tert-butyl-hydroxy phenyl) propanoic acid octadecyl, dilauryl thiodipropionate or the one or several of phosphorous acid benzene two isodecyl ester
Kind.The purpose of antioxidant is to reduce the degraded of polylactic acid during preparing composite and/or oxidation.
Described bulking agent is selected from polycaprolactone (PCL), in polyhydroxyalkanoate (PHA) or Polyethylene Glycol (PEG)
One or more.The purpose adding bulking agent is to reduce polylactic acid viscosity during melt extruding.
Described weather resisting agent selected from double (2,2,6,6-tetramethyl-4-piperidyl) sebacates, 2,4-dihydroxy-benzene first
In ketone, 2-(2 '-hydroxyl-5 '-) benzotriazole or 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole
One or more.
Described fire retardant is selected from magnesium hydroxide, aluminium hydroxide, APP, eight bromo ether, triphenyl phosphate, hexabromo ring ten
One or several in double (2, the 3-dibromopropyl) ether of dioxane, Firebrake ZB, encapsulated red phosphorus, TDE or tetrabromobisphenol A
Kind.
One or more in silicone oil, Polyethylene Glycol or low molecular weight polyethylene of described releasing agent.
Other described auxiliary agents are selected from 3-isooctyl mercaptopropionate, 4-diphenyl-4-methyl-1-pentene or 4,4-diformazan
Base-2, one or more in 4-diphenyl-1-butylene.
Described natural fiber has the feature that longer fibers length, after twisting, can present continuous state,
A branch of twisted fibers nominal count is 0.2～1, can be Z twist with the fingers to or S twist with the fingers to, its twist number range 50～200 twists/m.
Described natural fiber include hemp, cotton fiber, bamboo fibre, ramee, flax fiber, tossa,
Silk fiber and/or their hybrid yams, owing to lignin and hemicellulose are for the thermostability of the natural fiber as reinforcement
Can not be fully enhanced with mechanical properties strength, therefore natural fiber content of cellulose >=60%.
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
(1) by polylactic acid (PLA) resin 70～100 weight portion, antioxidant 0～5 weight portion, bulking agent 0～10 weight portion,
Weather resisting agent 0～3 weight portion, releasing agent 0～5 weight portion, fire retardant 0～5 weight portion, other auxiliary agent 0～2 weight portions are at blender
Middle mixing 3～7 minutes, join double screw extruder extrusion pelletizing after being sufficiently mixed, screw speed is 10～250r/min,
Extrusion temperature is 150～210 DEG C, obtains polydactyl acid (PLA) resin；
(2) natural fiber is through plasma, and alkali processes, and one or more in coupling agent treatment process, its medium from
It is to be irradiated in gamma-rays by natural fiber that daughter processes, and takes out；It is to put into natural fiber in alkaline bath to soak that alkali processes, alkaline bath
Concentration be 5～20g/l, through dealkalize, shake up, acid bath, washing, after baking step, available alkali process after natural fiber；
Coupling agent treatment is at surface of natural fibers coated with coupling agent, and through the natural fiber of coated with coupling agent, fiber surface tension force drops
Low, improve the compatibility with resin；Treated, its contact surface area increases, and interfacial adhesion strengthens, and surface can be changed
Kind, make matrix wellability good, improve the hot strength of composite；
(3) state that the natural fiber after processing still presents continuously and twists, then by natural fiber through untwisting
, there is the loose form expanded in machine untwisting；Different owing to preparing the fabric width of prepreg cloth, required natural fiber volume number is different, volume
Number scope is volume 1～200, the most preferably volume 50～150, more preferably volume 80～120；By the natural fiber after untwisting respectively from row
Cloth beaming appliance is drawn so that it is be uniformly distributed；Through traction and the direction controlling of direction-control apparatus, make natural fiber and pressure
There is between tight roller certain tension force, but tension force can not be too big, owing to natural fiber is after untwisting, if subjected to bigger
Tension force, easily disconnects；Natural fiber subsequently enters in the middle of hold-down roller, tenslator, and herein, natural fiber is compressed
The extruding of roller, loose natural fiber can be squeezed into the dipping of very thin one layer, beneficially natural fiber uniformly；
(4) polydactyl acid (PLA) resin that natural fiber is extruded with film extruder contacts and fills part dipping, now changes
The two sides of natural sex fiber is impregnated by property polylactic acid (PLA) resin；Through supercooling, it is fine that rolling i.e. prepares degradable natural
The composite material presoaked cloth of dimension/PLA.
A kind of device preparing degradable composite material prepreg cloth, including:
Unwinding machine, for carrying out untwisting to natural fiber；
Arrangement beaming appliance, for carrying out, to the natural fiber of knotting after untwisting, warping of arranging；
Direction-control apparatus, for being controlled the direction of the natural fiber through arrangement beaming appliance, makes by rear
The warp tension ratio of the natural fiber of continuous hold-down roller is more uniform；
Hold-down roller, for compressing fluffy natural fiber, makes natural fiber be uniformly distributed, the rotation linear speed of the first hold-down roller
Spending consistent with the rotational line speed putting yarn feeding device, the material of the first hold-down roller can be rubber, plastics；
Tenslator, enters the tension force of impregnation chiller, its rotational line speed and pressure for controlling natural fiber
The rotational line velocity magnitude of tight roller is the same, and the material of tenslator can be rubber, plastics；
Film extruder, for extrusion resin, extrudes substantial amounts of resin through modified PLA pellet by extruder, will
Natural fiber coating parcel, owing to the degradation temperature of natural fiber is more than 200 DEG C, for preventing the degraded of natural fiber and PLA,
The temperature range of extruder is 190～220 DEG C, and the weight of extrusion PLA per minute is 1～5kg, film width and natural fiber
Fabric width is the same, or than natural fiber fabric width wide 10～100mm；
Impregnation chiller, for impregnating natural fiber, and forms prepreg cloth, and impregnation chiller is by three rollers
Composition, is all steelwork, and natural fiber, through tenslator, enters between its first two pressure roll, and the inside is filled a large amount of
Resin, abundant extrusion impregnating, between thereafter two pressure rolls rolling flatten cooling, the rotational line speed of three rollers with
The rotational line speed of tenslator is the same；
Wrap-up, through impregnation, the prepreg cloth of cooling is in rolling herein, after its rotational line speed and impregnation chiller
The rotational line speed of two pressure rolls is the same.
Compared with prior art, the present invention has the following advantages and effect:
1, substantial amounts of polar group is contained due to the end group of natural fiber, same containing substantial amounts of hydroxyl in the strand of PLA
Based polar group, the interfacial bond property between natural fiber and PLA is better than the interfacial bond property between natural fiber and PP.
2, relatively low due to natural fiber oxygen index (OI), easily to burn, the self-extinguishment after PLA catches fire is good, generation gas during burning
The scale of construction is also few than polyester fiber, and is steam and carbon dioxide, little to environmental hazard.For harmful halogen family system and phosphorus system
Reduce etc. the demand of fire retardant of taking precautions against natural calamities, more can guarantee that safety and the environmental-protecting performance of material.
3, this preparation method, can adjust the content of natural fiber, prepares the preimpregnation of the reinforcing fiber of different content
Cloth.
4, select enhancing mutually and matrix is all Biodegradable material mutually, and derive from nature, little to environmental hazard,
Do not result in white pollution, meet the needs of sustainable development.
5, in the natural fiber/thermoplastic resin composite material presoaked belt of the present invention, phase natural fiber is strengthened with continuous phase
Existing, the enhancing in prepreg tape is unidirectional mutually, and when making product, mechanical property can be designed.
6, the composite longitudinal length that prepared by the present invention is adjustable, and wide cut can also be adjusted, and can meet the later stage
Length requirement in production.
7, the present invention prepare composite can be with long storage time, and natural fiber is impregnated by resin completely, the most naked
Exposing outside, material especially natural fiber can be kept to be dried, natural fiber will not moldy metamorphism.
8, the present invention can limit the fabric width of reinforcing material, because of wide or narrow, and will not make the position of natural fiber
Change.
9, the method for the present invention can ensure that resin thorough impregnation natural fiber, and resin thorough impregnation natural fiber is permissible
Ensureing during preparing product, the defect of product is few, and mechanical strength is high.
10, to prepare the porosity of prepreg tape relatively low for the present invention, less than 1%, the when that porosity being low, can guarantee that properties of product
Stability.
Accompanying drawing explanation
Fig. 1 is present invention process flow process and device schematic diagram.
Wherein 1 for opening twister；2 is natural fiber arrangement apparatus；3 is natural fiber；4 fill for natural fiber direction controlling
Put；5,5 ' is natural fiber hold-down roller (speed can not be the highest)；6,6 ' is that natural fiber changes direction device；7 extrude for film
Machine；8 is wrap-up；9,9 ', 9 " it is impregnation chiller.
Wherein 1 is unwinding machine, and the product commercially produced due to natural fiber passes through twisting so that it is become continuous state
Existing, natural fiber is after twisting, and resin is not easy dipping, if the product of excellent, it is necessary to after twisting
Natural fiber untwisting；
Wherein 2 is natural fiber arrangement apparatus, and natural fiber, after untwisting, is easily tied a knot, it is necessary to strict control moves back
The arrangement of natural fiber after sth. made by twisting, so utilizing this device fixing little for natural fiber scope；
Wherein 3 is natural fiber, and natural fiber has been arranged side by side certain fabric width herein, the volume number of fabric width and natural fiber
Relevant；
Wherein 4 is natural fiber direction-control apparatus, natural fiber after arrangement apparatus 2, the motion of natural fiber
The little scope of track fixing, but natural fiber from arrangement apparatus out after, distance 5,5 ' hold-down rollers distant, fiber
When arriving hold-down roller, tension force is uneven.Utilize 4 these devices that the direction of natural fiber is controlled so that it is by compressing
During roller, the tension force of all natural fibers is essentially the same, promotes natural fiber uniformly to arrange；
Wherein 5,5 ' is a pair hold-down roller, and the material of hold-down roller can be rubber herein, and (this type of material is being subject to plastics etc.
During to bigger pressure, it may occur that deformation, natural fiber will not rupture because of extruding herein).Natural fiber after shredding,
Tow is fluffy, and the effect of hold-down roller herein compresses fluffy natural fiber exactly, makes natural fiber be uniformly distributed, turning of hold-down roller
Moving-wire speed is consistent with the rotational line speed putting yarn feeding device；
Wherein 6,6 ' also a pair hold-down roller, the most also have an another one effect, namely natural fiber
Force control device, the material of hold-down roller herein can be rubber, and (this type of material, when by bigger pressure, can be sent out for plastics etc.
Change shape, and natural fiber will not rupture because of extruding herein).Natural fiber has presented and has been uniformly distributed herein, and fluffy
Pine state changes.Utilize the tension force control action of 6,6 ', change the tension force of natural fiber, mainly control natural fiber and enter
Enter 9 " and the tension force of 9 ', the rotational line speed of hold-down roller now is the same with the rotational line velocity magnitude of 5,5 ' hold-down rollers；
Wherein 7 is film extruder, extrudes substantial amounts of resin by extruder, by natural through modified PLA pellet
Fiber coating parcel, owing to the degradation temperature of natural fiber is more than 200 DEG C, for preventing the degraded of natural fiber and PLA, extrusion
The temperature range of machine is 190～220 DEG C, and the weight of extrusion PLA per minute is 1～5kg, film width and the fabric width of natural fiber
Equally, or than natural fiber fabric width wide 10～100mm；
Wherein 9,9 ', 9 " being impregnation chiller, 3 rollers herein are all steelwork；Natural fiber is through 6,6 ' places
Tension force control, enter 9 ' and 9 " between pressure roll, substantial amounts of resin, abundant extrusion impregnating are filled in the inside, roll through 9 and 9 '
Flatten cooling.9,9 ', 9 " rotational line speed is the same with the rotational line speed of 6,6 '；
Wherein 8 is wrap-up, through impregnation, the prepreg cloth of cooling in rolling herein, its rotational line speed and 9,9 '
Rotational line speed the same.
It addition, the hold-down roller shown in Fig. 1 includes 5,5 ', 6,6 ', and in order to improve properties of product, and continue the pressure added
Tight roller, namely hold-down roller not only includes two couple shown in Fig. 1, it is three right to have, and four is right, and five is right, by that analogy.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, and in embodiment, the content of component is weight portion.
Embodiment 1
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
By PLA resin 70 parts, dilauryl thiodipropionate 5 parts, polyhydroxyalkanoate 10 parts, double (2,2,6,6-tetra-
Methyl-4-piperidyl) sebacate 3 parts, Polyethylene Glycol 5 parts, Firebrake ZB 5 parts, 3-isooctyl mercaptopropionate 1 part, 4,4-diformazans
Base-2,4-diphenyl-1-butylene 1 part mixes 7 minutes in a mixer, joins double screw extruder extrusion after being sufficiently mixed
Pelletizing, screw speed is 80r/min, and extrusion temperature is 205 DEG C, obtains modified PLA resin；The performance test results is shown in Table 1.
By volume 120 of the tossa after Cement Composite Treated by Plasma, through unwinding machine untwisting, the loose shape expanded occurs
State, processes each step in embodiment 1 of the tossa after untwisting, wherein the resin of extrusion in film extruder
For the PLA resin that above-mentioned steps is modified, its extrusion temperature is 190 DEG C.Natural fiber is made to impregnate with PLA two sides, through supercool
But, rolling, the tossa/PLA composite material prepreg of Wholly-degradable can be prepared.The performance test results is shown in
Embodiment 2
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
Take PLA resin 82 parts, phosphorous acid benzene two isodecyl ester 4 parts, Polyethylene Glycol 7 parts, 2-(2 '-hydroxyl-5 '-) benzo three
Azoles 2 parts, aluminium hydroxide 2 parts, 3 parts of magnesium hydroxide mixes 4 minutes in a mixer, joins in double screw extruder after mixing,
Extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
By volume 80 of the flax fiber after Cement Composite Treated by Plasma, through unwinding machine untwisting, the loose form expanded occurs,
The flax fiber after untwisting each step in embodiment 1 being processed, wherein in film extruder, the resin of extrusion is
Above-mentioned modified PLA resin, its extrusion temperature is 210 DEG C.Natural fiber is made to impregnate with PLA two sides, through supercooling, rolling,
Flax fiber/PLA the composite material prepreg of Wholly-degradable can be prepared.The performance test results is shown in Table 1.
Embodiment 3
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
Take PLA resin 85 parts, dilauryl thiodipropionate 1 part, polyhydroxyalkanoate (PHA) 2 parts, 2,4-dihydroxies
Base-benzophenone 1 part, TDE 2 parts, HBCD 3 parts, silicone oil 5 parts, 4-diphenyl-4-methyl-1-pentene 1
Part, mixing 6 minutes in material mixer, join after mixing in double screw extruder, extruding pelletization, screw speed is 75r/
Min, extruder head temperature is 190 DEG C.The tossa volume 150 that alkali of learning from else's experience in the present embodiment processes is opened through opening twister 1
Twist with the fingers, the natural fiber 3 after opening sth. made by twisting, the most i.e. tossa, be placed on natural fiber arrangement apparatus 2, through natural fibre
After dimension direction controlling 4, enter natural fiber hold-down roller 5,5 ', be then passed through natural fiber direction and change device 6,6 ', through this
Several steps, it is 0.9mm that tossa becomes thin a layer thickness, then the dipping of PLA resin in film extruder 7, its
Middle PLA resin is modified resin prepared by above-mentioned steps, at impregnation chiller 9,9 ', 9 " dipping cooling after, enter at rolling 8
Row rolling.Prepare Corchorus olitorius L./polylactic acid prepreg tape.The performance test results is shown in Table 1.
Embodiment 4
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
Take PLA resin 87 parts, four { β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid } pentaerythritol ester 2 parts, gather in oneself
Ester 5 parts, and 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole 2 parts, low molecular weight polyethylene 2 parts, phosphorus
Triphenyl phosphate ester 2 parts mixes 4 minutes in material mixer, joins in double screw extruder, extruding pelletization after mixing, and screw rod turns
Speed is 75r/min, and extruder head temperature is 190 DEG C.The tossa volume 100 that alkali of learning from else's experience in the present embodiment processes is through opening
Twister 1 opens sth. made by twisting, the natural fiber 3 after opening sth. made by twisting, the most i.e. tossa is placed on natural fiber arrangement apparatus 2, passes through
After natural fiber direction controlling 4, enter natural fiber hold-down roller 5,5 ', be then passed through natural fiber direction and change device 6,6 ',
Through these steps, it is 0.9mm that tossa becomes thin a layer thickness, then the leaching of PLA resin in film extruder 7
Stain, wherein PLA resin is modified resin prepared by above-mentioned steps, at impregnation chiller 9,9 ', 9 " after dipping cooling, in rolling
Rolling is carried out at 8.Prepare Corchorus olitorius L./polylactic acid prepreg tape.The performance test results is shown in Table 1.
Embodiment 5
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
Take PLA resin 90 parts, (3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecyl 3 parts, double (2,2,6,6-tetra-
Methyl-4-piperidyl) sebacate 2 parts, APP 5 parts, mix 6 minutes in material mixer, join double after mixing
In screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.Learn from else's experience in the present embodiment
The tossa volume 100 crossing alkali process opens sth. made by twisting through opening twister 1, the natural fiber 3 after opening sth. made by twisting, the most i.e. tossa,
It is placed on natural fiber arrangement apparatus 2, after natural fiber direction controlling 4, enters natural fiber hold-down roller 5,5 ', then
Change device 6,6 ' through natural fiber direction, through these steps, it is 0.9mm that tossa becomes thin a layer thickness,
The dipping of PLA resin in film extruder 7 again, wherein PLA resin is modified resin prepared by above-mentioned steps, cold at impregnation
Radiator cooler 9,9 ', 9 ", after dipping cooling, at rolling 8, rolling is carried out.Prepare Corchorus olitorius L./polylactic acid prepreg tape.Performance test is tied
Fruit is shown in Table 1.
Embodiment 6
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
Take PLA resin 95 parts, dilauryl thiodipropionate 2 parts, double 2 parts of (2, the 3-dibromopropyl) ether of tetrabromobisphenol A, eight
Bromo-ether 1 part, mixes 6 minutes in material mixer, joins in double screw extruder, extruding pelletization, screw speed after mixing
For 75r/min, extruder head temperature is 190 DEG C.The tossa volume 100 that alkali of learning from else's experience in the present embodiment processes is through opening sth. made by twisting
Sth. made by twisting left by machine 1, the natural fiber 3 after opening sth. made by twisting, the most i.e. tossa is placed on natural fiber arrangement apparatus 2, Jing Guotian
After so machine direction controls 4, enter natural fiber hold-down roller 5,5 ', be then passed through natural fiber direction and change device 6,6 ', warp
Crossing these steps, it is 0.9mm that tossa becomes thin a layer thickness, then the leaching of PLA resin in film extruder 7
Stain, wherein PLA resin is modified resin prepared by above-mentioned steps, at impregnation chiller 9,9 ', 9 " after dipping cooling, in rolling
Rolling is carried out at 8.Prepare Corchorus olitorius L./polylactic acid prepreg tape.The performance test results is shown in Table 1.
Embodiment 7
A kind of preparation method of degradable composite material prepreg cloth, this preparation method comprises the following steps:
By volume 100 of the sisal fiber after Cement Composite Treated by Plasma, take PLA resin 100 parts, through unwinding machine untwisting, go out
Now the loose form expanded, processes each step in embodiment 1 of the sisal fiber after untwisting, wherein film extrusion
In machine, the resin of extrusion is pure PLA resin, and its extrusion temperature is 190 DEG C.Make natural fiber impregnate with PLA two sides, pass through
Cooling, rolling, the sisal fiber/PLA composite material prepreg of Wholly-degradable can be prepared.The performance test results is shown in Table 1.
Table 1
Corchorus olitorius L. content the most herein utilizes densimetry to test
Its method of testing is as follows: utilize air-discharging method to test tossa density respectively for ρFiber, resin density is ρResin, in advance
Leaching band density is ρPrepreg tape, utilize formula C=(ρResin-ρPrepreg tape)/(ρResin-ρFiber), calculate fiber content.
Hot strength testing standard in table 1 is GB/T3354-1999, and oxygen index (OI) testing standard is GB8924.
Application examples
The preimpregnated cloth that will produce, cuts into variously-shaped, puts in mould, through melted heating, pressurization, prepares
Phone housing.This kind of phone housing impact resistance, and after discarding, recovery of well degrading, effect on environment is little.
The present invention untwisting by natural fiber, roll-in is in blocks so that it is be sufficiently spread out, in gumming device, by launch
Natural fiber, carries out resin dipping to its two sides, and to improve the dipping effect of natural fiber, resin now is molten condition
PLA, obtains laminate through supercooling, rolling.The internals that can make by thermoplastic resin with molding, the inside of such as vehicle
Component, the phone housing that can alternately change, the recovery problem of other non-degradable resins can be solved.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.
These embodiments obviously readily can be made various amendment by person skilled in the art, and described herein typically
Principle is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, this
Skilled person should be at the protection model of the present invention according to the announcement of the present invention, the improvement made for the present invention and amendment
Within enclosing.
Claims (6)
1. a degradable composite material prepreg cloth, this composite material presoaked cloth includes polydactyl acid (PLA) resin, natural fibre
Dimension, wherein polydactyl acid (PLA) resin accounts for the percentage by weight of composite material presoaked cloth is 40～70%；
Described degradable composite material prepreg cloth prepares by the following method:
(1) by polylactic acid (PLA) resin 70～100 weight portion, antioxidant 0～5 weight portion, bulking agent 0～10 weight portion, weather-proof
Agent 0～5 weight portion, releasing agent 0～5 weight portion, fire retardant 0～5 weight portion, other auxiliary agent 0～5 weight portions mix in a mixer
Closing 3～7 minutes, join double screw extruder extrusion pelletizing after being sufficiently mixed, screw speed is 10～250r/min, extrusion
Temperature is 150～210 DEG C, obtains polydactyl acid (PLA) resin；Wherein antioxidant, solubilizing agent, weather resisting agent, releasing agent, fire-retardant
It is 0 when agent is different with other auxiliary agents；
(2) natural fiber processes through plasma, alkali, and one or more in coupling agent treatment process, its plasma
Process is to be irradiated in gamma-rays by natural fiber, takes out；It is to put into natural fiber in alkaline bath to soak that alkali processes, alkaline bath dense
Degree is 5～20g/l, through dealkalize, shake up, acid bath, washing, after baking step, available alkali process after natural fiber；Coupling
It is at surface of natural fibers coated with coupling agent that agent processes, and through the natural fiber of coated with coupling agent, fiber surface tension force reduces, changes
The kind compatibility with resin；Treated, its contact surface area increases, and interfacial adhesion strengthens, and surface can be improved, be made base
Body wellability is good, improves the hot strength of composite；
(3) state that the natural fiber after processing still presents continuously and twists, then moves back natural fiber through unwinding machine
Twist with the fingers, the loose form expanded occurs；Different owing to preparing the fabric width of prepreg cloth, required natural fiber volume number is different, rolls up number model
Enclose is volume 1～200；Natural fiber after untwisting is drawn respectively from arrangement beaming appliance so that it is be uniformly distributed；Through direction
Control traction and the direction controlling of device, make that there is between natural fiber and hold-down roller certain tension force, but tension force can not be too big,
Owing to natural fiber is after untwisting, if subjected to bigger tension force, easily disconnect；Natural fiber subsequently enter hold-down roller,
In the middle of tenslator, herein, natural fiber is extruded by hold-down roller, and loose natural fiber can be extruded uniformly
Become very thin one layer, the beneficially dipping of natural fiber；
(4) polydactyl acid (PLA) resin that natural fiber is extruded with film extruder contacts and is sufficiently impregnated with, now modified poly-
The two sides of natural sex fiber is impregnated by lactic acid (PLA) resin；Through supercooling, rolling i.e. prepares degradable natural fiber/PLA
Composite material presoaked cloth；
Described antioxidant is selected from four { β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid } pentaerythritol ester, (3,5-bis-tertiary fourths
Base-4-hydroxy phenyl) propanoic acid octadecyl, the one or several in dilauryl thiodipropionate or phosphorous acid benzene two isodecyl ester
Kind；
Described bulking agent is selected from polycaprolactone (PCL), the one in polyhydroxyalkanoate (PHA) or Polyethylene Glycol (PEG)
Or it is several；
Described weather resisting agent selected from double (2,2,6,6-tetramethyl-4-piperidyl) sebacates, 2,4-dihydroxy-benzophenone, 2-
In (2 '-hydroxyl-5 '-) benzotriazole or 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole one
Plant or several；Described fire retardant is selected from magnesium hydroxide, aluminium hydroxide, APP, eight bromo ether, triphenyl phosphate, hexabromo ring
One or several in double (2, the 3-dibromopropyl) ether of dodecane, Firebrake ZB, encapsulated red phosphorus, TDE or tetrabromobisphenol A
Kind；One or more in silicone oil, Polyethylene Glycol or low molecular weight polyethylene of described releasing agent；Other described auxiliary agents
In 3-isooctyl mercaptopropionate, 4-diphenyl-4-methyl-1-pentene or 4,4-dimethyl-2,4-diphenyl-1-butylene
One or more.
A kind of degradable composite material prepreg cloth the most according to claim 1, it is characterised in that described polydactyl acid
(PLA) melt index of resin is 10～40g/10min, and viscous equal molecular mass is 1～10 × 105g/mol。
A kind of degradable composite material prepreg cloth the most according to claim 1, it is characterised in that described natural fiber tool
Having longer fibers length, after twisting, can present continuous state, a branch of twisted fibers nominal count is 0.2～1, permissible
Be Z twist with the fingers to or S twist with the fingers to, its twist number range 50～200 twists/m.
A kind of degradable composite material prepreg cloth the most according to claim 1, it is characterised in that described natural fiber bag
Include hemp, cotton fiber, bamboo fibre, ramee, flax fiber, tossa and/or their hybrid yams, the most natural
Fiberoptic fiber cellulose content >=60%.
5. a preparation method for degradable composite material prepreg cloth, this preparation method comprises the following steps:
(1) by polylactic acid (PLA) resin 70～100 weight portion, antioxidant 0～5 weight portion, bulking agent 0～10 weight portion, weather-proof
Agent 0～5 weight portion, releasing agent 0～5 weight portion, fire retardant 0～5 weight portion, other auxiliary agent 0～5 weight portions mix in a mixer
Closing 3～7 minutes, join double screw extruder extrusion pelletizing after being sufficiently mixed, screw speed is 10～250r/min, extrusion
Temperature is 150～210 DEG C, obtains polydactyl acid (PLA) resin；Wherein antioxidant, solubilizing agent, weather resisting agent, releasing agent, fire-retardant
It is 0 when agent is different with other auxiliary agents；
(2) natural fiber processes through plasma, alkali, and one or more in coupling agent treatment process, its plasma
Process is to be irradiated in gamma-rays by natural fiber, takes out；It is to put into natural fiber in alkaline bath to soak that alkali processes, alkaline bath dense
Degree is 5～20g/l, through dealkalize, shake up, acid bath, washing, after baking step, available alkali process after natural fiber；Coupling
It is at surface of natural fibers coated with coupling agent that agent processes, and through the natural fiber of coated with coupling agent, fiber surface tension force reduces, changes
The kind compatibility with resin；Treated, its contact surface area increases, and interfacial adhesion strengthens, and surface can be improved, be made base
Body wellability is good, improves the hot strength of composite；
(3) state that the natural fiber after processing still presents continuously and twists, then moves back natural fiber through unwinding machine
Twist with the fingers, the loose form expanded occurs；Different owing to preparing the fabric width of prepreg cloth, required natural fiber volume number is different, rolls up number model
Enclose is volume 1～200；Natural fiber after untwisting is drawn respectively from arrangement beaming appliance so that it is be uniformly distributed；Through direction
Control traction and the direction controlling of device, make that there is between natural fiber and hold-down roller certain tension force, but tension force can not be too big,
Owing to natural fiber is after untwisting, if subjected to bigger tension force, easily disconnect；Natural fiber subsequently enter hold-down roller,
In the middle of tenslator, herein, natural fiber is extruded by hold-down roller, and loose natural fiber can be extruded uniformly
Become very thin one layer, the beneficially dipping of natural fiber；
(4) polydactyl acid (PLA) resin that natural fiber is extruded with film extruder contacts and is sufficiently impregnated with, now modified poly-
The two sides of natural sex fiber is impregnated by lactic acid (PLA) resin；Through supercooling, rolling i.e. prepares degradable natural fiber/PLA
Composite material presoaked cloth.
6. prepare a device for degradable composite material prepreg cloth, including:
Unwinding machine, for carrying out untwisting to natural fiber；
Arrangement beaming appliance, for carrying out, to the natural fiber of knotting after untwisting, warping of arranging；
Direction-control apparatus, for being controlled the direction of the natural fiber through arrangement beaming appliance, makes by follow-up pressure
The warp tension ratio of the natural fiber of tight roller is more uniform；
Hold-down roller, for compressing fluffy natural fiber, makes natural fiber be uniformly distributed, the rotational line speed of the first hold-down roller with
The rotational line speed putting yarn feeding device is consistent, and the material of the first hold-down roller is rubber or plastics；
Tenslator, enters the tension force of impregnation chiller, its rotational line speed and hold-down roller for controlling natural fiber
Rotational line velocity magnitude the same, the material of tenslator is rubber or plastics；
Film extruder, for extrusion resin, extrudes substantial amounts of resin by extruder, by natural through modified PLA pellet
Fiber coating parcel, owing to the degradation temperature of natural fiber is more than 200 DEG C, for preventing the degraded of natural fiber and PLA, extrusion
The temperature range of machine is 190～220 DEG C, and the weight of extrusion PLA per minute is 1～5kg, film width and the fabric width of natural fiber
Equally, or than natural fiber fabric width wide 10～100mm；
Impregnation chiller, for impregnating natural fiber, and forms prepreg cloth, and impregnation chiller is by three roller groups
Becoming, be all steelwork, natural fiber, through tenslator, enters between its first two pressure roll, and the inside is filled substantial amounts of
Resin, abundant extrusion impregnating, between thereafter two pressure rolls rolling flatten cooling, the rotational line speed of three rollers with
The rotational line speed of force control device is the same；
Wrap-up, through impregnation, the prepreg cloth of cooling in rolling herein, after its rotational line speed and impregnation chiller two
The rotational line speed of pressure roll is the same.
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| CN104228237B (en) * | 2013-06-07 | 2018-09-21 | 上海杰事杰新材料(集团)股份有限公司 | Natural fiber enhances the preparation method of thermoplastic composite material prepreg slide plate plate face |
| CN109651782B (en) * | 2018-12-11 | 2020-12-22 | 黄河科技学院 | Preparation method of composite plant fiber biodegradable material |
| CN110983799A (en) * | 2019-12-23 | 2020-04-10 | 清远市齐力合成革有限公司 | Soft wet base for synthetic leather and manufacturing method thereof |
| CN111621040B (en) * | 2020-06-09 | 2022-11-18 | 贵州大学 | Method for reducing heat generation of butadiene styrene rubber vulcanized rubber, product and preparation method thereof |
| CN111703043B (en) * | 2020-06-30 | 2021-04-27 | 哈尔滨坤程科技有限公司 | Carbon fiber PLA composite wire and preparation process thereof |
| CN114395232B (en) * | 2022-01-25 | 2023-08-15 | 广东盈尔实业有限公司 | Processing method of degradable packaging film and degradable packaging film |
| CN115958841B (en) * | 2022-12-28 | 2023-10-20 | 宜兴威尼特集装袋有限公司 | Preparation process of laminated valve pocket |
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| CN101003667A (en) * | 2006-01-20 | 2007-07-25 | 东丽纤维研究所（中国）有限公司 | Composite material of poly lactic acid / natural faric, and production method |
| CN101619199A (en) * | 2008-07-03 | 2010-01-06 | 李俊辉 | Manufacture technique of easy tear tape |
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| CN101619199A (en) * | 2008-07-03 | 2010-01-06 | 李俊辉 | Manufacture technique of easy tear tape |
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Denomination of invention: Biodegradable composite prepreg cloth, and preparation method and device for the same Effective date of registration: 20191202 Granted publication date: 20160928 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980000815 |